CN105503571B - A kind of copper complex formazan preparation method of lead citrate - Google Patents
A kind of copper complex formazan preparation method of lead citrate Download PDFInfo
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- CN105503571B CN105503571B CN201510887362.1A CN201510887362A CN105503571B CN 105503571 B CN105503571 B CN 105503571B CN 201510887362 A CN201510887362 A CN 201510887362A CN 105503571 B CN105503571 B CN 105503571B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/44—Lead
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- Oil, Petroleum & Natural Gas (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention belongs to organic chemical industry's synthesis field, specifically related to a kind of lead citrate copper complex preparation method, the preparation method is using trisodium citrate aqueous solution as substrate, under ul-trasonic irradiation, successively be added dropwise etc. carboxyl equivalent nitrate aqueous solution, question response thing is separated out, and is then heated rapid draing through heating, reaction aging, centrifugation and microwave coupling steam, is obtained uniform double-base rocket solid catalyst citric acid lead bronze.The present invention takes citric acid and lead, the nitrate of copper directly to react, will not introduce the pollution of other compositions, utilizes mechanical agitation and ultrasonic wave-coupled effect, it is to avoid product precipitation sandwiches raw material or accessory substance sodium nitrate, makes product uniformly pure；Drying takes microwave coupling steam to heat rapid draing mode, it is to avoid the drawbacks of traditional drying " outer burnt in tender " causes nature difference inside and outside product；Using the copper-lead ratio of different proportion, a technique can obtain a series of catalyst of different properties.
Description
Technical field
The invention belongs to organic chemical industry's synthesis field, and in particular to a kind of lead citrate copper complex preparation method.
Background technology
Citric acid lead bronze is double base propellant burningrate catalyst, and it is synthesized there is not yet document report.Citric acid lead bronze is complexed
Thing preparation method be new technology and various instruments, means it is integrated.
Double base propellant burningrate catalyst is important national defence articles for use, is widely used in the equipment such as rocket, guided missile.Double base propellant
Burn rate is low, and burning rate exponent is high, so burningrate catalyst must be added, to improve its burning velocity.Double base propellant burn rate is catalyzed
Agent, can improve the promotion effect of propellant, pushing body is launched along optimal trajectory, and can reduce the nitrogen oxidation after propellant combustion
The content of compound, the content of increase nitrogen reduces the corrosion to pushing body, reduces the pollution to air, has very to enhancement of environment
Significance.Since the seventies, the state such as America and Europe does not send out and develops the burningrate catalyst of many kinds of propellants in succession.
On probation according to user, citric acid lead bronze can improve propellant as double base propellant burningrate catalyst newly developed
Effect is promoted, pushing body is launched along optimal trajectory, and the content of the oxynitrides after propellant combustion can be reduced, increases nitrogen
The content of gas reduces the corrosion to pushing body, reduces the pollution to air.
The content of the invention
The present invention provides a kind of lead citrate copper complex preparation method, using trisodium citrate aqueous solution as substrate, ultrasound
Under ripple effect, the nitrate aqueous solution of the carboxyl equivalent such as dropwise addition, question response thing is separated out, and then temperature reaction is aged, centrifugation, microwave
Coupling steam heats rapid draing, obtains uniform double-base rocket solid catalyst：Citric acid lead bronze；When plumbi nitras, copper nitrate
When ratio changes, a series of different catalyst of performance because of the change of lead bronze ratio are obtained.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of lead citrate copper complex preparation method, the described method comprises the following steps：
1) it is 1 mole of (3 work as quantity carboxylic acid) trisodium citrate is soluble in water, 50 ± 3 DEG C are heated to, is filtered standby；
2) n/2 moles of (n equivalents) plumbi nitras is dissolved in water, is heated to 45 ± 3 DEG C, filter standby, wherein 0<n<3；
3) (3-n)/2 mole (3-n equivalents) copper nitrate is dissolved in water, is heated to 45 ± 3 DEG C, filter standby, wherein 0<n<
3；
4) by step 1) obtained trisodium citrate aqueous solution temperature maintains 50 ± 3 DEG C, sequentially adds step 2) nitre
Lead plumbate solution and step 3) copper nitrate solution；
5) feed and finish, be warming up to 85 ± 3 DEG C, reaction aging 6Hr；
6) 45 ± 5 DEG C, centrifugal solid-liquid separation are cooled to；
7) solid crude product is washed with 45 ± 2 DEG C of deionized waters to nitrate anion and is less than 3ppm；
8) after the heated drying of wet product, the rocket solid catalyst that moisture is less than 0.05% is obtained：Citric acid lead bronze.
Be used as further optimization, the step 1) in sodium citrate equivalent be equal to step 2) in plumbi nitras and step 3) in nitre
Sour equivalent thickness of copper sum.
As further optimization, the sodium citrate can on the spot be synthesized by citric acid hydrogenation aqueous solution of sodium oxide.
Be used as further optimization, the step 4) in addition lead nitrate solution and copper nitrate solution process, in ultrasonic wave and
Carried out under mechanical agitation coupling.
Be used as further optimization, the step 5) in reaction aging carried out under ultrasonic wave and mechanical agitation coupling.
Be used as further optimization, the step 6) in cooling procedure carried out under ultrasonic wave and mechanical agitation coupling.
Be used as further optimization, the step 8) in wet product heat drying mode be microwave coupling steam heating.
It is used as further optimization, described 0<n<3, when n changes, obtain a series of lead bronze ratios differences and performance is variant
Lead citrate copper catalyst.
Beneficial effects of the present invention：
The present invention takes citric acid and lead, the nitrate of copper directly to react, and will not introduce other composition pollutions；Utilize stirring
With ultrasonic wave-coupled effect, it is to avoid product precipitation sandwiches raw material or accessory substance sodium nitrate, makes product uniformly pure；Drying is taken
Microwave coupling steam heats rapid draing mode, it is to avoid traditional drying " outer burnt in tender " causes the disadvantage of nature difference inside and outside product
End；Using the copper-lead ratio of different proportion, a technique can obtain a series of catalyst of different properties.
Embodiment
In order that present invention is easier and is expressly understood, below according to specific embodiment, the present invention is made into one
Step detailed description.
A kind of lead citrate copper complex preparation method, using trisodium citrate aqueous solution as substrate, under ul-trasonic irradiation, according to
Nitrate (plumbi nitras and copper nitrate) aqueous solution of the carboxyl equivalents such as secondary dropwise addition, reactant is separated out, then through heating up, reacting old
Change, rapid draing is heated in centrifugation and microwave coupling steam, obtains uniform double-base rocket solid catalyst citric acid copper-lead；Work as nitre
When lead plumbate, the change of copper nitrate ratio, a series of different catalyst of performance because of the change of lead bronze ratio are obtained.
Embodiment 1：
1) it is 1 mole of (3 work as quantity carboxylic acid) trisodium citrate is soluble in water, 50 ± 3 DEG C are heated to, is filtered standby；
2) 0.75 mole of (1.5 equivalent) plumbi nitras is dissolved in water, is heated to 45 ± 3 DEG C, filtered standby；
3) 0.75 mole of (1.5 equivalent) copper nitrate is dissolved in water, is heated to 45 ± 3 DEG C, filtered standby；
4) by step 1) the obtained temperature of trisodium citrate aqueous solution maintains 50 ± 3 DEG C, stirred in ultrasonic wave and machinery
Mix under coupling, sequentially add step 2) lead nitrate solution and step 3) copper nitrate solution；
5) feed and finish, be warming up to 85 ± 3 DEG C, the reaction aging 6Hr under ultrasonic wave and mechanical agitation coupling；
6) it is cooled to 45 ± 5 DEG C, centrifugal solid-liquid separation under ultrasonic wave and mechanical agitation coupling；
7) solid crude product, which is washed with 45 ± 2 DEG C of deionized waters to nitrate anion, is less than 3ppm；
8) wet product obtains the rocket solid catalyst that moisture is less than 0.05% after microwave coupling steam heat drying：Lemon
Lemon lead plumbate copper, yield 91%, lead bronze ratio is 1:1.
Embodiment 2：
1) it is 1 mole of (3 work as quantity carboxylic acid) trisodium citrate is soluble in water, it is heated to 50 ± 3 DEG C, it is standby after filtering；
2) 1 mole of (2 equivalent) plumbi nitras is dissolved in water, is heated to 45 ± 3 DEG C, filtered standby；
3) 0.25 mole of (1 equivalent) copper nitrate is dissolved in water, is heated to 45 ± 3 DEG C, filtered standby；
4) by step 1) the obtained temperature of trisodium citrate aqueous solution maintains 50 ± 3 DEG C, stirred in ultrasonic wave and machinery
Mix under coupling, sequentially add step 2) lead nitrate solution and step 3) copper nitrate solution；
5) feed and finish, be warming up to 85 ± 3 DEG C, the reaction aging 6Hr under ultrasonic wave and mechanical agitation coupling；
6) under ultrasonic wave and mechanical agitation coupling, it is cooled to 45 ± 5 DEG C, centrifugal solid-liquid separation；
7) solid crude product, which is washed with 45 ± 2 DEG C of deionized waters to nitrate anion, is less than 3ppm；
8) wet product obtains the rocket solid catalyst that moisture is less than 0.05% after microwave coupling steam heat drying：Lemon
Lemon lead plumbate copper, yield 91.5%, lead bronze ratio is 2:1.
Embodiment 3：
1) it is 1 mole of (3 work as quantity carboxylic acid) trisodium citrate is soluble in water, 50 ± 3 DEG C are heated to, is filtered standby；
2) 0.3 mole of (0.6 equivalent) plumbi nitras is dissolved in water, is heated to 45 ± 3 DEG C, filtered standby；
3) 1.2 moles of (2.4 equivalent) copper nitrates are dissolved in water, are heated to 45 ± 3 DEG C, filtered standby；
4) by step 1) the obtained temperature of trisodium citrate aqueous solution maintains 50 ± 3 DEG C, stirred in ultrasonic wave and machinery
Mix under coupling, sequentially add step 2) lead nitrate solution and step 3) copper nitrate solution；
5) feed and finish, be warming up to 85 ± 3 DEG C, the reaction aging 6Hr under ultrasonic wave and mechanical agitation coupling；
6) under ultrasonic wave and mechanical agitation coupling, it is cooled to 45 ± 5 DEG C, centrifugal solid-liquid separation；
7) solid crude product, which is washed with 45 ± 2 DEG C of deionized waters to nitrate anion, is less than 3ppm；
8) wet product obtains the rocket solid catalyst that moisture is less than 0.05% after microwave coupling steam heat drying：Lemon
Lemon acid copper-lead, yield 91%, lead bronze ratio is 1:4.
Particular embodiments described above, has been carried out further in detail to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail it is bright, should be understood that the foregoing is only the present invention specific embodiment, be not intended to limit the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., should be included in the guarantor of the present invention
Within the scope of shield.
Claims (4)
1. a kind of lead citrate copper complex preparation method, it is characterised in that the described method comprises the following steps：
1) it is 1 molar citric acid trisodium is soluble in water, 50 ± 3 DEG C are heated to, is filtered standby；
2) n/2 molar nitric acid lead is dissolved in water, is heated to 45 ± 3 DEG C, filter standby, wherein 0<n<3；
3) the molar nitric acid copper of (3-n)/2 is dissolved in water, is heated to 45 ± 3 DEG C, filter standby, wherein 0<n<3；
4) by step 1) obtained trisodium citrate aqueous solution temperature maintains 50 ± 3 DEG C, sequentially adds step 2) plumbi nitras
Solution and step 3) copper nitrate solution, addition lead nitrate solution and copper nitrate solution process, in ultrasonic wave and mechanical agitation coupling
Cooperation is carried out under；
5) feed and finish, be warming up to 85 ± 3 DEG C, reaction aging 6Hr, reaction aging enters under ultrasonic wave and mechanical agitation coupling
OK；
6) 45 ± 5 DEG C are cooled to, centrifugal solid-liquid separation, cooling procedure is carried out under ultrasonic wave and mechanical agitation coupling；
7) solid crude product is washed with 45 ± 2 DEG C of deionized waters to nitrate anion and is less than 3ppm；
8) after the heated drying of wet product, the rocket solid catalyst that moisture is less than 0.05% is obtained：Citric acid lead bronze, wet product heating
Drying mode heats for microwave coupling steam.
2. a kind of lead citrate copper complex preparation method according to claim 1, it is characterised in that：The step 1) in
Sodium citrate equivalent be equal to step 2) in plumbi nitras and step 3) in nitric acid equivalent thickness of copper sum.
3. a kind of lead citrate copper complex preparation method according to claim 1, it is characterised in that：The sodium citrate
Can on the spot it be synthesized by citric acid hydrogenation aqueous solution of sodium oxide.
4. a kind of lead citrate copper complex preparation method according to claim 1, it is characterised in that：Described 0<n<3, when
When n changes, a series of lead bronze ratios differences and the discrepant lead citrate copper catalyst of performance are obtained.
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| CN201510887362.1A CN105503571B (en) | 2015-12-04 | 2015-12-04 | A kind of copper complex formazan preparation method of lead citrate |
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| CN201510887362.1A CN105503571B (en) | 2015-12-04 | 2015-12-04 | A kind of copper complex formazan preparation method of lead citrate |
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| CN105503571B true CN105503571B (en) | 2017-10-17 |
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| GB2152920B (en) * | 1983-08-12 | 1987-06-24 | Secr Defence | Propellant composition |
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| CN102059142B (en) * | 2010-11-27 | 2012-07-25 | 中北大学 | Method for preparing copper plumbum chelate/mesoporous carbon composite material |
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Effective date of registration: 20190516 Address after: No. 1600 Yuegong Road, Jinshan District, Shanghai, 201507 Patentee after: Shanghai Wokai Biotechnology Co., Ltd. Address before: 200072 No. 801 Hutai Road, Zhabei District, Shanghai Patentee before: Sinopharm Chemical Reagent Co., Ltd. |
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